2,5-Diaryl-N-[2-(allylthio)phenyl]pyrroles and
2,5-diaryl-N-[2-(allyloxy)phenyl]pyrroles 26
6.56 (1H, m) and 6.33 (1H, m); m/z 143 (M+, 100%), 116 (16)
and 115 (47) (spectra consistent with literature data28): 2-phenyl-
1H-dibenzo[2,3:6,7]thiepino[4,5-b]pyrrole 34a (0.163 g, 19%) mp
Using the method reported above, the derivatives 26 were made
by treatment of the appropriate N-arylpyrrole (1 equivalent) and
allyl bromide (1.1 equivalents) with a suspension of potassium
carbonate (1.1 equivalents) in DMF (10 cm3 per gram of pyrrole).
After TLC showed the absence of starting material, the product
was isolated by aqueous work-up and purified by bulb to bulb
distillation. Other products made by this method are described in
the ESI.†
124–127 ◦C dH 9.15 (1H, br. s), 8.69 (2H, m), 8.26 (1H, d, J
3
8.0), 8.04 (1H, d, 3J 7.9) and 7.77-7.33 (10H, m); dC 135.43
(quat), 132.30 (quat), 129.27 (quat), 128.94, 128.27 (quat), 127.08,
126.71, 126.47, 126.02 (quat), 124.60, 124.15, 123.90, 123.67
(quat), 123.34, 123.27, 122.79 (quat), 122.10 (quat), 119.61 and
100.37 (2 CH signals overlapping); m/z (FAB) 326 [(M+1)+, 8%),
294 [(M+1-32)]+ 100: 1-phenyl-2H-dibenzo[2,3:6,7]thiepino[4,5-
c]pyrrole 36a (0.026 g, 3%) mp 130–135 ◦C dH 9.11 (1H, br. s),
8.73-8.65 (2H, m), 8.12 (1H, m), 7.94 (1H, m), 7.65-7.32 (9H, m)
2,5-Diphenyl-N-[2-(allylthio)phenyl]pyrrole 26a
3
and 7.10 (1H, d, J 2.6); dC 137.02 (quat), 130.05, 128.88 (quat),
128.23, 126.72, 126.50, 126.16, 124.66, 123.76 (2 CH), 123.33,
122.93 (quat), 122.21 (quat), 120.97 and 119.50 (1 CH and 4
quaternaries not assigned); m/z 293 [(M-32)+, 2%], 205 (7), 143
(9), 98 (6), 97 (9), 94 (33), 86 (100), 84 (33) and 83 (42).
2,5-Diphenyl-N-(2-mercaptophenyl)pyrrole 25a (3.27 g, 0.01 mol)
gave 2,5-diphenyl-N-[2-(allylthio)phenyl]pyrrole 26a (3.52 g,
96%), mp 120–122 ◦C (from ethanol) (Found. C, 81.3; H, 5.6; N,
3.65. C25H21NS requires C, 81.7; H, 5.75; N, 3.8%); dH 7.27–7.05
(14H, m), 6.56 (2H, s), 5.57 (1H, m), 5.02-4.93 (2H, m) and 3.29
(2H, m); dC 137.50 (quat), 137.05 (quat), 135.87 (quat), 133.01,
132.69, 130.74 (quat), 130.48, 128.32, 128.11 (4CH), 127.65 (4CH),
126.07 (2CH), 125.36, 117.68, 109.48 (2CH) and 34.80; m/z 367
(M+, 100%), 327 (17), 326 (72), 223 (15), 119 (40) and 115 (11).
FVP of 2,5-di-p-tolyl-N[2-(allylthio)phenyl]pyrrole 26b
FVP of 2,5-di-p-tolyl-N[2-(allylthio)phenyl]pyrrole 26b [0.80 g,
(2.0 mmol), Tf 650 ◦C, Ti 235 ◦C, P 0.005 Torr, t 15 min]
gave a mixture of products which were initially separated by
dry-flash column chromatography (1% ethyl acetate–hexane:
2.5% gradient) to give the first and last components of the
mixture. The other fractions were combined and re-columned
(1% ethyl acetate–hexane: no gradient). The following products
were obtained: 2-methyldibenzothiophene 30b (0.032 g, 8%)
FVP of 2,5-diphenyl-N-[2-(allylthio)phenyl]pyrrole 26a
FVP of 2,5-diphenyl-N-[2-(allylthio)phenyl]pyrrole 26a [0.98 g,
(2.7 mmol) Tf 750 ◦C, Ti 220 ◦C, P 0.01 Torr, t 40 min] gave
a mixture which was separated by dry-flash chromatography
(hexane). The following seven products wer◦e identified: diben-
zothiophene 30a (0.046 g, 9%) mp 95–98 C (lit.,26 99.7 ◦C)
dH 8.22-8.14 (2H, m), 7.94–7.85 (2H, m) and 7.53–7.46 (4H,
m); dC 139.32 (quat), 135.43 (quat), 126.60, 124.25, 122.71 and
121.48; (NMR spectra consistent with literature data27); m/z 184
(M+, 100%), 139 (22), 92 (38) and 79 (19): 1-phenylpyrrolo[2,1-
◦
mp 78–81 C (lit.,29 86 ◦C); dH 8.13 (1H, m), 7.97 (1H, m),
3
7.85 (1H, m), 7.74 (1H, d, J8.2), 7.48–7.41 (2H, m), 7.28 (1H,
m) and 2.55 (3H, s); dC 139.67 (quat), 136.26 (quat), 135.56
(quat), 135.30 (quat), 133.97 (quat), 128.08, 126.39, 124.06,
122.69, 122.28, 121.64, 121.33 and 21.37 (spectra compatible
with literature values30); m/z 198 (M+, 100%), 195 (19), 152 (13)
and 98 (13): 1-p-tolylpyrrolo[2,1-b]benzothiazole 31b (0.015 g,
3%) (Found: M+, 263.0776. C17H13NS requires M 263.0769); dH
(360 MHz) 7.61 (1H, m), 7.48–7.43 (2H, m), 7.33–7.30 (3H, m),
◦
b]benzothiazole 31a (0.033 g, 5%) mp 110–113 C (Found: M+
249.0612. C16H11NS requires M 249.0612) dH 7.60–7.09 (9H,
m), 6.52 (1H, d, 3J 3.6) and 6.32 (1H, d, 3J 3.6); dC 135.09
(quat), 132.79 (quat), 131.73 (quat), 129.33, 128.53 (quat), 128.26,
127.55, 124.62, 123.56, 123.16, 115.66, 113.46 and 99.00 (one
quaternary overlapping); m/z 249 (M+, 59%), 248 (100), 125
(18), 124 (30) and 115 (30): 1-phenyldibenzo[b,f ]pyrrolo[1,2-d]-
1,4-thiazepine 32a (0.038 g, 4%) mp 89–93 ◦C [Found (FAB):
(M+H)+ 326.1003. C22H16NS requires M 326.1003] dH 8.34–8.24
3
3
7.21–7.11 (2H, m), 6.50 (1H, d, J 3.6), 6.32 (1H, d, J 3.7) and
2.49 (3H, s); dC (90 MHz) 138.01 (quat), 135.77 (quat), 132.34
(quat), 130.46 (quat), 129.91, 129.52, 128.83 (quat), 128.71 (quat),
125.15, 124.07, 123.64, 115.91, 114.03, 99.41 and 30.75; m/z 263
(M+, 100%), 261 (34), 205 (22), 130 (18), 129 (18), 128 (21) and 91
(12): 6-methyl-1-p-tolyldibenzo[b,f ]pyrrolo[1,2-d]-1,4-thiazepine
32b (0.12 g, 17%) (Found: M+, 353.1236. C24H19NS requires M
353.1238); dH (360 MHz) 8.30 (1H, m), 8.03 (1H, s), 7.92 (1H, d,
3J 8.1), 7.52–7.08 (8H, m), 6.96 (1H, m), 6.59 (1H, m), 2.51 (3H,
s) and 2.44 (3H, s); dC (90 MHz) 137.58 (quat), 135.88 (quat),
134.75 (quat), 133.41 (quat), 131.94 (quat), 131.74 (quat), 129.92,
129.75, 129.36, 127.37, 125.72 (quat), 124.93 (quat), 124.29,
124.80 (quat) 123.89, 123.06, 122.88, 119.41, 116.17, 101.80,
22.24 and 21.79; m/z 353 (M+, 75%), 321 (100), 305 (21), 193
(27), 152 (23), 119 (30) and 91 (21): 4-methyl-1-(5-p-tolylpyrrol-
2-yl)dibenzothiophene) 33b (0.24 g, 34%) (Found: M+, 353.1233.
C24H19NS requires M 353.1238); dH (360 MHz) 8.46 (1H, br.
3
4
(2H, m), 8.07 (1H, dd, J 7.7, J 1.2), 7.57–7.11 (10H, m), 7.08
3
3
(1H, d, J 3.9) and 6.69 (1H, d, J 3.9); dC 135.54 (quat), 133.89
(quat), 131.47 (quat), 131.38 (quat), 128.82, 128.50, 128.05, 127.31,
126.98, 126.62 (quat), 125.83, 125.19 (quat), 123.85, 123.52, 122.98
(quat), 122.54, 122.27, 118.92, 115.94 and 102.04; m/z (FAB) 326
[(M+H)+, 100%]: 4-(5-phenylpyrrol-2-yl)dibenzothiophene 33a
◦
(0.210 g, 24%) mp 115–118 C (Found: M+ 325.0911. C22H15NS
requires M 325.0925) dH 8.68 (1H, br. s), 7.88 (2H, m), 7.55-
7.22 (10H, m), 6.78 (1H, m) and 6.49 (1H, m); dC 140.01 (quat),
139.49 (quat), 135.10 (quat), 132.40 (quat), 131.41 (quat), 130.00
(quat), 128.85, 128.20, 127.91 (quat), 127.62, 126.38, 126.21,
125.85, 124.24, 123.58, 122.52, 109.83 and 107.00 (two CH signals
overlapping); m/z 325 (M+, 100%), 323 (23), 220 (11) and 163
(13): mixture of which the main component was 2-phenylpyrrole
35a (0.043 g, ca. 11%) (Found: M+ 143.0735. C10H9N requires M
143.0735) dH 8.43 (1H, br. s), 7.70–7.15 (5H, m), 6.83 (1H, m),
3
3
s), 7.91 (1H, d, J 7.9), 7.47-7.20 (9H, m), 6.72 (1H, t, J 3.1),
3
6.47 (1H, t, J 3.0), 2.69 (3H, s) and 2.40 (3H, s); dC (90 MHz)
140.65 (quat), 139.83 (quat), 136.44 (quat), 134.09 (quat), 132.93
(quat), 132.47 (quat), 131.64 (quat), 130.37 (quat), 130.06,
128.53, 128.27 (quat), 126.76, 126.73, 124.88, 124.80, 124.12,
This journal is
The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 5173–5183 | 5181
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